1,2,3-Thiadiazole-5-carboxylic acid amide derivatives, process for making the same and herbicidal growth regulating defoliating and fungicidal compositions containing same

ABSTRACT

1,2,3-Thiadiazole-5-carboxylic acid amide derivatives of the formula ##STR1## wherein R 1 , R 2  and R 3  have the meaning indicated in the specification. Preferably, R 1  is methyl and R 2  is acetyl, chloroacetyl, propionyl, valeryl, cinnamoyl, cyclohexylcarbonyl, dichlorophenoxyacetyl, benzoyl, halobenzoyl, dichlorobenzoyl or methylbenzoyl, and R 3  is benzyl, halobenzyl, cyclohexyl, methyl-cyclohexyl or cyclohexylmethyl. The compounds have herbicidal, growth regulating, defoliating and fungicidal activity, although not all of these activities will be present in each of the compounds. The compounds are in addition highly selective against agriculturally valuable plants such as various grains, cotton, soybeans and plantation cultures.

BACKGROUND OF THE INVENTION

The invention relates to 1,2,3-thiadiazole-5-carboxylic acid amidederivatives, a process for making the same and agents containing thesame and having a herbicidal, growth regulating and defoliating as wellas fungicidal activity.

In the area of plant production the weed control must meet threeessential functions: it must safeguard the yields, assure the ultimateusefulness of the harvested products, and improve the working andproduction conditions. Modern weed control in many cases is theprerequisite for the complete mechanization of an organizational line orat least enables the possibility for the introduction of new techniques.Changes produced thereby have a strong effect on agricultural andhorticultural operations. There is therefore heavy demand for bothgeneral as well as specific technical advances in the area ofherbicides. This is particularly so because the heretofore known agentsof this type do not fully comply with the requirements.

It is, therefore, an object of the present invention to provide for anagent which permits an improvement of the technique of weed control.

ESSENCE OF THE INVENTION

This object is met by an agent which at least contains one compound ofthe formula ##STR2##

In this formula

R₁ is hydrogen or an alkyl group which in its chain may have one orseveral oxygen or sulfur atoms and which may be substituted by halogen,

R₂ is hydrogen or C₁ to C₁₈ -alkyl, C₂ to C₈ -alkenyl, C₂ to C₈-alkinyl, aryl-C₁ to C₃ -alkyl, all of which group may also besubstituted, or is a C₃ -C₈ -cycloaliphatic hydrocarbon group which mayalso be substituted or in which there may be attached by condensation anaromatic or cycloaliphatic ring, or R₂ may be a C₃ -C₈ -cycloalkyl-C₁-C₃ -alkyl group which may also be substituted. R₂ may further be anaromatic hydrocarbon residue which may be substituted in one or severalplaces by C₁ -C₆ -alkyl and/or halogen and/or C₁ -C₆ -alkoxy and/ornitro and/or trifluoromethyl.

R₃ is hydrogen or one of the following radicals which may also besubstituted: C₁ -C₁₈ -alkyl, C₂ -C₈ -alkenyl, aryl-C₁ -C₃ -alkyl or a C₃-C₈ -cycloaliphatic hydrocarbon residue to which may be attached bycondensation one or more aromatic or cycloaliphatic rings. R₃ mayfurthermore be an aromatic hydrocarbon residue which may also besubstituted in one or several places by C₁ -C₆ -alkyl and/or C₁ -C₆-alkoxy and/or nitro and/or trifluoromethyl or R₃ may be C₁ -C₆ -alkoxy,C₃ -C₆ -alkenyloxy or alkinyloxy or it may be aryloxy which may also besubstituted, or C₁ -C₄ -alkylthio or arylthio which latter may also besubstituted. R₃ may further be an amino group of the formula ##STR3## inwhich R₄ and R₅ are the same or different and are hydrogen, C₁ -C₆-alkyl, aryl or is aryl which may be substituted in one or severalplaces by the same or different radicals selected from the groupconsisting of C₁ -C₆ -alkyl, halogen, C₁ -C₆ -alkoxy, nitro and/ortrifluoromethyl.

These compositions surprisingly have a superior herbicidal activity,when applied to the soil or leaves, on seed weeds and resistant weedsand surpass the heretofore known compositions of an analogousconstitution and a similar kind of activity.

The action of the compositions is partly systemic. They are particularlyuseful against dicotyledonous and monocotyledonous weeds of the generaDigitalis, Trifolium Portulaca, Papaver, Daucus, Kochia, Gypsophila,Lactuca, Solanum, Eschholtzia, Cheiranthus, Phacelia, Euphorbia, Linum,Convolvulus, Brassica, Datura, Cichorium, Ipomoea, Setaria, Agrostis,Phleum, Alopecurus, Phalaris, Dactylis, Festuca, Arrhenaterum, Lolium,Bromus, Avena, Allium, Cucumis, Medicago, Stellaria, Senecio,Matricaria, Lamium, Centaurea, Amaranthus, Galium, Chrysanthemum,Polygonum, Sorghum, Echinochloa, Digitaria, Cyperus, Poa and otherweeds.

The amounts in which the compositions are employed against weeds areabout 0.5 to 5.0 kg active agent per ha, 1 ha being equal to about 2.54acres.

A selective weed control is for instance possible in cultures comprisingcereals, cotton, soybeans and plantation cultures. These compositionshave their greatest effect if they are applied by spraying to an emergedweed but may also be applied prior to its emergence. The weed culturescan also be drilled a few days after spraying.

The compositions may also be used to modify the natural development ofthe plants to obtain certain properties which may be useful inagricultural or horticultural respects. It will, however, be understoodthat not each composition has the same regulating effects with each typeof plant, type of application, time of application or concentration ofapplication.

The compounds of the invention can be applied to seeds, seedlings, prioror after emergence, to roots, stems, leaves, blossoms, fruits or otherparts of the plants.

The control of the natural growth in general can be visually determinedby modifications of the size, shape, color or structure of the treatedplants or their parts.

By way of examples the following development changes of the plants maybe effected by use of the compositions of the invention:

Enlargement of the leaf

Inhibition of the vertical growth

Inhibition of the root development

Stimulation of bud sprouting or the sprouting of plant stocks

Intensifying of the formation of plant dyestuffs

Defoliation.

It has also been found that the compounds of the invention are effectiveagainst various fungicidal pests, for instance of the genera Botrytis,Cercospora, Erysiphe, Helminthosporium, Piricularia, Plasmoparpa,Tilletia and others.

This has the advantage that simultaneously with the regulation of theplant growth a control of fungi which are pathogenic to the plants canbe accomplished which is of substantial technical importance.

The compounds of the invention can be used either by themselves or inmixture with each other or in mixture with other active agents. Ifdesired, other defoliating or plant protection agents or pesticides maybe added as desired.

Should it be desirable to broaden the spectrum of the activity it ispossible to add other biocidal agents. For instance, herbicidally activeadded agents may be added from the group of the triazines,aminotriazoles, anilides, diazines, uraciles, aliphatic carboxylic orhalogenated carboxylic acids, substituted benzo acids and aryloxycarboxylic acids, hydrazides, amides, nitriles, esters of suchcarboxylic acids, carbamic- and thiocarbamic acid esters, ureaderivatives, 2,3,6-trichlorobenzyloxypropanil, rhodan containing agentsand other additives. Among further additives there may be named alsonon-phytotoxic additives which result in a synergistic increase of theactivity with herbicides such as among others, wetting agents,emulsifiers, solvents, and oily additives.

The compounds of the invention or their mixtures are preferably used inthe form of compositions such as powders, dusting agents, granulates,solutions, emulsions or suspensions and upon addition of liquid and/orsolid carrier materials or diluents. If desired, wetting, adhesion,emulsification and/or dispersion promoting agents may be added.

Suitable liquid carrier materials are, for instance, water, aliphaticand aromatic hydrocarbons, such as, benzene, toluene, xylone,cyclohexanone, isophorone, dimethylsulfoxide, dimethylformamide, andfurthermore mineral oil fractions.

As solid carrier materials there are suited mineral earths, forinstance, tonsil, silicagel, talc, kaolin, attaclay, limestone, silicicacid and plant products such as flours.

As surface active agents which may be added there may be mentioned forinstance calciumlignosulfonate, polyoxyethylene-alkylphenolether,naphthalene sulfonic acids and their salts, phenol sulfonic acids andtheir salts, formaldehyde condensation products, fatty alcohol sulfatesas well as substituted benzosulfonic acids and their salts. Theproportion of the agent or agents may be varied within broad ranges. Thecompositions may, for instance, contain about 5 to 95% by weight ofactive agents, about 95 to 5% by weight of liquid or solid carriermaterials and, if desired, up to 20% by weight of surface active agentswhich would then reduce the amount of other carrier materials.

The application of the agents can be effected in conventional manner,for instance with water as the carrier material, in spray amounts ofabout 100 to 5000 1/ha. The application of the agents can be effectedboth in the so-called low volume and so-called ultra low volume processor also in the form of so-called micro granulates.

PREFERRED EMBODIMENTS

In the compounds indicated above by Formula 1, the different R radicalsmay, for instance, be:

R₁ may be hydrogen or C₁ -C₄ -alkyl, which may also be substituted, forinstance, methyl, ethyl, propyl, chloromethyl, bromomethyl,methylthiomethyl, methoxymethyl.

R₂ may be hydrogen or C₁ -C₁₈ -alkyl, for instance methyl, ethyl,propyl, isopropyl, n-butyl, tert-butyl, 2,2-dimethyl-1-propyl, n-heptyl,n-nonyl, n-undecyl, n-octadecyl, 3-methylbutyl, 4-methyl-2-pentyl,isobutyl, 3,3-dimethylbutyl, 2-butyl, or 3,3-dimethyl-2-butyl;subsituted C₁ -C₁₈ -alkyl, for instance, 2-chloroethyl, 3-chloropropyl,3-bromopropyl, 2-bromoethyl, 1-phenoxy-2-propyl, 3-dimethylaminopropyl,2-dimethylaminoethyl, 3-diethylaminopropyl, tetrahydrofurfuryl,ethoxycarbonylmethyl, cyanomethyl, 2,2-dimethoxyethyl or 2-ethoxyethyl;C₃ -C₈ cycloalkyl-C₁ -C₃ -alkyl, for instance, cyclohexylmethyl,4-cyanocyclohexylmethyl, 4-hydroxymethylcyclohexylmethyl,4-carboxylcyclohexylmethyl, 1-hydroxycyclohexylmethyl,cycloheptylmethyl, cyclooctylmethyl or cyclopropylmethyl; C₂ -C₈-alkenyl- or -alkinyl, for instance, 2-propenyl, 2-butenyl,2-methyl-2-propenyl, 2-propinyl or 3-ethyl-1-pentyne-3-yl, aryl-C₁ -C₃-alkyl, for instance, benzyl, 4-chlorobenzyl, 3-chlorobenzyl,2-chlorobenzyl, 4-fluorobenzyl, 3-fluorobenzyl, 2-fluorobenzyl,4-methylbenzyl, 3-methylbenzyl, 2-methylbenzyl, 3,4-methylendioxybenzyl,2,4-dichlorobenzyl, 3,4-dichlorobenzyl, 4-methoxybenzyl,3-methoxybenzyl, 2-methoxybenzyl, 2-pyridylmethyl, 3-pyridylmethyl,4-pyridylmethyl, α,α,dimethylbenzyl, 1-phenylethyl, 2-phenylethyl,1,2-diphenylethyl, 2,2-diphenylethyl, 4-fluoro-α-methoxybenzyl,3-phenylpropyl or 2-furfuryl; C₃ -C₈ -cycloaliphatic hydrocarbonresidue, for instance, cyclopropyl, cyclopentyl, cyclohexyl,2-methylcyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl,1,2,3,4-tetrahydro-1-naphthyl, 1-ethinylcyclohexyl, cycloheptyl orcyclooctyl; aromatic hydrocarbon residues, for instance, phenyl,3-chlorophenyl, 2-chlorophenyl, 4-chlorophenyl, 2,4-dichlorophenyl,4-fluorophenyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 1-naphthyl, 2-methoxyphenyl, 3-methoxyphenyl or 4-nitrophenyl.

R₃ may for instance comprise in case of the C₁ -C₁₈ -alkyl groups:methyl, ethyl, propyl, isopropyl, n-butyl, 1-ethylpropyl, tert-butyl,n-heptyl, n-nonyl, n-undecyl, n-octadecyl, 3,3-dimethylpropyl; in caseof the substituted C₁ -C₁₈ -alkyl groups: chloromethyl, fluoromethyl,bromomethyl, 2-chloroethyl, 1-chloroethyl, dichloromethyl,trichloromethyl, 1-bromoethyl, phenoxymethyl,(2,4-dichlorophenoxy)-methyl, 1-phenoxyethyl, 2-phenoxyethyl; in case ofthe C₂ -C₈ -alkenyl groups: vinyl, 2-butenyl, 2-methyl-2 -propenyl,propene-1-yl, 2-phenylvinyl; in case of the C₃ -C₈ -cycloaliphatichydrocarbon groups: cyclopropyl, cyclopentyl, cyclohexyl,methylcyclohexyl; in case of the aliphatic-aromatic hydrocarbon groups:benzyl, 4-chlorobenzyl, 1-phenylethyl, 2-phenylethyl; in case of thearomatic hydrocarbon groups: phenyl, 2-chlorophenyl, 4-chlorophenyl,3-chlorophenyl, 2,6-dichlorophenyl, 2,4-dichlorophenyl, 2-methylphenyl,3-methylphenyl, 4-methylphenyl, 3-nitrophenyl, 4-nitrophenyl,2-methoxyphenyl, 4-methoxyphenyl, 1-naphthyl, 2-naphthyl or 2-furyl; incase of the C₁ -C₆ -alkoxy groups: methoxy, ethoxy, propoxy, isopropoxy,n-butoxy; in case of the C₃ -C₆ -alkenyl- or -alkinyloxy groups:2-propeneyloxy, 2-buteneyloxy, 2 -propinyloxy; in case of the aryloxygroups: phenoxy or 4-chlorophenoxy; in case of the arylthio groups:phenylthio or 4-chlorophenylthio; in case of the C₁ -C₄ -alkylthiogroups: methylthio, ethylthio, propylthio; in case of the amino groups:methylamino, dimethylamino, ethylamino, diethylamino, anilino,N-methylanilino or 4-chloranilino.

Among the compounds of the invention those having a particularlysuperior herbicidal and growth regulating activity are those where inthe above formula of the 1,2,3-thiadiazole-5-carboxylic acid amidederivatives the individual R groups are the following:

R₁ methyl

R₃ CO acetyl, chloroacetyl, propionyl, valeryl, cinnamoyl,cyclohexylcarbonyl, dichlorophenoxyacetyl, benzoyl, halobenzoyl,dichlorobenzoyl or methylbenzoyl

R₂ benzyl, halobenzyl, cyclohexyl, methylcyclohexyl or cyclohexylmethyl.

PROCESS OF MAKING

The compounds which so far have not been found in the literature can bemade in various ways. In all of the processes presently to be described,R₁, R₂, and R₃ have the same meaning as in the above first-mentionedFormula I, while X is halogen, preferably chlorine and B is a univalentmetal equivalent, preferably sodium, potassium or lithium.

Useful processes are the following:

(A) Metal compounds of the formula ##STR4## are reacted with acylhalides of the formula

    R.sub.3 --CO--X.

(B) 1,2,3-thiadiazole-5-carboxylic acid amides of the formula ##STR5##are reacted in the presence of acid acceptors with acyl halides of theformula

    R.sub.3 --CO--X

(C) 1,2,3-thiadiazole-5-carboxylic acid amides of the formula ##STR6##are reacted with acid anhydrides of the formula

    R.sub.3 --CO--O--CO--R.sub.3

which reaction may be carried out in the presence of a catalyst such assulfuric acid, p-toluenesulfonic acid or pyridine

(D) 1,2,3-thiadiazole-5-carboxylic acid amides of the formula ##STR7##are reacted with isopropenyl compounds of the formula ##STR8## whichreaction may also be carried out in the presence of a catalyst such assulfuric acid, p-toluene sulfonic acid or pyridine,

(E) 1,2,3-thiadiazole-5-carboximidochlorides of the formula ##STR9## arereacted with carboxylic acids of the formula

    R.sub.3 --CO--OH

in the presence of an acid acceptor,

(F) Metal compounds of the formula ##STR10## are reacted with1,2,3-thiadiazole-5-carboxylic acid halides of the formula ##STR11##

(G) Amides of the formula ##STR12## are reacted in the presence of acidacceptors with 1,2,3-thiadiazole-5-carboxylic acid halides of theformula ##STR13## or

(H) Imidochlorides of the formula ##STR14## are reacted with1,2,3-thiadiazole-5-carboxylic acids of the formula ##STR15## in thepresence of acid acceptors.

In all these cases the reaction should be carried out at a temperaturebetween 0° and 120° C., preferably between room temperature and thereflux temperature of the reaction mixture.

For the synthesis the reactants are preferably used in about equimolaramounts. Suitable reaction media are solvents which are inert in respectof the reactants. The selection of the solvents or suspension agentsdepends on the type of acyl halides, acid acceptors and metal compoundsused.

As solvents or suspension agents there may for instance be mentioned thefollowing: ethers like diethylether, tetrahydrofuran and dioxane;aliphatic and aromatic hydrocarbons, like petroleum ether, cyclohexane,benzene, toluene and xylene; carbonic acid nitriles, like acetonitrile,or ketones, like acetone.

As acid acceptors organic bases may be used, for instance triethylamineor N,N-dimethylaniline and pyridine bases or inorganic bases, likeoxides, hydroxides and carbonates of alkaline earth and alkalimetals.Liquid bases like pyridine can also simultaneously be used as solvents.

The compounds made by any of the above processes can then be isolated inconventional form, for instance by distilling off the solvent atatmospheric or reduced pressure or by precipitation with water.

The compounds of the invention normally are colorless and nonsmellingcrystalline substances or colorless and nonsmelling liquids which have apoor solubility in water, a moderate solubility in aliphatichydrocarbons, such as petroleum ether and cyclohexane and a goodsolubility in halogenated hydrocarbons, such as chloroform and carbontetrachloride; aromatic hydrocarbons, like benzene, toluene, xylene;ethers, like diethylether, tetrahydrofuran, and dioxane; carboxylic acidnitriles, like acetonitrile; ketones, like acetone; alcohols, likemethanol and ethanol; carboxylic acid amides, like dimethylformamide andsulfoxides, like dimethylsulfoxides.

As solvents for the recrystallization there are preferred cyclohexane,acetonitrile and diisopropylether.

The starting products for making the compounds of the invention areknown or can be made by an obvious procedure on the basis of the knownprocesses.

EXAMPLES OF COMPOUNDS AND OF THE PROCESS OF MAKING

The following examples will further illustrate the making of thecompounds of the invention and give certain examples of specificcompounds.

EXAMPLE 1 4-methyl-1,2,3-thiadiazole-5-carboxylicacid-(N-acetyl-N-cyclohexylmethyl)-amide

16.8 g (0.07 mol) of 4-methyl-1,2,3-thiadiazole-5-carboxylicacid-(cyclohexylmethyl)-amide were suspended in 35 ml (0.32 mol) aceticacid isopropenyl ester and were reacted then with 0.04 ml concentratedsulfuric acid. The mixture was subsequently heated for 28 hours uponreflux. The remaining oil was crystallized with 50 ml of pentane.Recrystallization was effected with cyclohexane.

The yield was 14.7 g=74.6% of the theoretical value.

M.p.: 73°-74° C.--colorless crystals.

EXAMPLE 2 4-methyl-1,2,3-thiadiazole-5-carboxylicacid-(N-benzoyl-N-cyclohexylmethyl)-amide

A solution of 23.9 g (0.1 mol) of4-methyl-1,2,3-thiadiazole-5-carboxylic acid-(cyclohexylmethyl)-amide)in 200 ml of tetrahydrofuran was mixed with 2.4 g (0.1 mol) sodiumhydride and maintained for 2 hours at reflux temperature. There werethen added at 0°-10° C. upon cooling 14.06 g (0.1 mol) ofbenzoylchloride. After a reaction time of 2 hours the solution wasconcentrated and the resulting residue was cautiously reacted withwater. Subsequently it was several times shaken out with ether. Theether extracts were dried on magnesium sulfate and concentrated and theremaining crystals were recrystallized from isopropyl ether.

The yield was 13.0 g-38% of the theoretical value

M.p.: 89°-91° C.--colorless crystals.

EXAMPLE 3 4-methyl-1,2,3-thiadiazole-5-carboxylicacid-(N-isobutyryl-N-cyclohexylmethyl)-amide

4.7 ml (0.05 mol) of isobutyric acid in 50 ml tetrahydrofuran werecaused to boil with 7.1 ml (0.05 mol) of triethylamine. There were thenadded dropwise at the reflux temperature 12.9 g (0.05 mol)4-methyl-1,2,3-thiadiazole-5-(N-cyclohexylmethylcarboximidochloride)dissolved in 100 ml tetrahydrofuran. The mass was then further heatedupon reflux for 15 minutes. It was then permitted to cool; theprecipitate was filtered off and the organic phase was concentrated. Theremaining oil was taken up in ether and several times shaken out withwater. The ether phase which had been dried on magnesium sulfate wasconcentrated and the remaining oil was dried in a vacuum at 40° C.

Yield: 11.0 g-71.2% of the theoretical value

n_(D) ²⁰ : 1.5291--colorless oil.

The following compounds of the invention were made in an analogousmanner.

    ______________________________________                                        Compound                Physical constants                                    ______________________________________                                        4-methyl-1,2,3-thiadiazole-5-                                                 carboxylic acid-(N-benzoyl-N-                                                 benzyl)-amide           m.p.: 95-97° C.                                4-methyl-1,2,3-thiadiazole-5-                                                 carboxylic acid-[N-benzoyl-N-                                                 (4-fluorobenzyl]-amide  m.p.: 143-44° C.                               4-methyl-1,2,3-thiadiazole-5-                                                 carboxylic acid-[N-benzoyl-N-(2-                                              methylcyclohexyl)]-amide                                                                              m.p.: 99-102° C.                               4-methyl-1,2,3-thiadiazole-5-                                                 carboxylic acid-[N-acetyl-N-(2-                                               fluorobenzyl)]-amide    n.sub.D.sup.20 : 1,5627                               4-methyl-1,2,3-thiadiazole-5-                                                 carboxylic acid-[N-acetyl-N-(4-                                               fluorobenzyl)]-amide    n.sub.D.sup.20 : 1,5625                               4-methyl-1,2,3-thiadiazole-5-                                                 carboxylic acid-[N-acetyl-N-(4-                                               chlorobenzyl)]-amide    m.p.: 66-68° C.                                4-methyl-1,2,3-thiadiazole-5-                                                 carboxylic acid-[N-(4-chlorobenzo-                                            yl-)-N-cyclohexylmethyl]-amide                                                                        m.p.:115-16° C.                                4-methyl-1,2,3-thiadiazole-5-                                                 carboxylic acid-(N-propionyl-N-                                               cyclohexylmethyl)-amide m.p.: 64-65° C.                                4-methyl-1,2,3-thiadiazole-5-                                                 carboxylic acid-[N-(4-fluorobenzo-                                            yl)-N-cyclohexylmethyl]-amide                                                                         m.p.: 110-11° C.                               4-methyl-1,2,3-thiadiazole-5-                                                 carboxylic acid-(N-chloroacetyl-                                              N-cyclohexylmethyl)-amide                                                                             m.p.: 111-12° C.                               4-methyl-1,2,3-thiadiazole-5-                                                 carboxylic acid-[N-(3-chlorobenzo-                                            yl)-N-cyclohexylmethyl]-amide                                                                         m.p.: 96-97° C.                                4-methyl-1,2,3-thiadiazole-5-                                                 carboxylic acid-[N-(3-methylbenzo-                                            yl) N-cyclohexylmethyl]-amide                                                                         m.p.: 73-74° C.                                4-methyl-1,2,3-thiadiazole-5-                                                 carboxylic acid-[N-(4-methylbenzo-                                            yl)-N-cyclohexylmethyl]-amide                                                                         m.p.: 71-72° C.                                4-methyl-1,2,3-thiadiazole-5-                                                 carboxylic acid-(N-valeryl-N-cy-                                              clohexylmethyl)-amide   m.p.: 46-47° C.                                4-methyl-1,2,3-thiadiazole-5-                                                 carboxylic acid-[N-(2,4-dichloro-                                             phenoxyacetyl)-N-cyclohexyl-                                                  methyl]-amide           m.p.: 87-89° C.                                4-methyl-1,2,3-thiadiazole-5-                                                 carboxylic acid-(N-benzoyl-N-cy-                                              clohexyl)-amide         m.p.: 81-83° C.                                4-methyl-1,2,3-thiadiazole-5-                                                 carboxylic acid-(n-acetyl-N-cyclo-                                            hexyl)-amide            m.p.: 82-83° C.                                4-methyl-1,2,3-thiadiazole-5-                                                 carboxylic acid-[N-(2-chlorobenzo-                                            yl)-N-cyclohexylmethyl]-amide                                                                         m.p.: 53-55° C.                                4-methyl-1,2,3-thiadiazole-5-                                                 carboxylic acid-(N-cinnamoyl-N-                                               cyclohexylmethyl)-amide n.sub.20.sup.20 : 1,5947                              4-methyl-1,2,3-thiadiazole-5-                                                 carboxylic acid-(N-cyclohexylcar-                                             bonyl-N-cyclohexylmethyl)-amide                                                                       m.p.: 96-97° C.                                4-methyl-1,2,3-thiadiazole-5-                                                 carboxylic acid-(N-cyclohexylmethyl-                                          N-cyclopropylcarbonyl)-amide                                                                          n.sub.D.sup.20 : 1,5411                               4-methyl-1,2,3-thiadiazole-5-                                                 carboxylic acid[N-cyclohexylmethyl-                                           N-(2,6-dichlorobenzoyl)]-amide                                                                        m.p.: 81-83° C.                                4-methyl-1,2,3-thiadiazole-5-                                                 carboxylic acid-(N-cyclohexylmetnyl-                                          N-dichloroacetyl)-amide m.p.: 84-86° C.                                4-methyl-1,2,3-thiadiazole-5-                                                 carboxylic acid-(N-crotonoyl-N-                                               cyclohexylmethyl)-amide n.sub.D.sup.20 : 1,5478                               4-methyl-1,2,3-thiadiazole-5-                                                 carboxylic acid-[N-cyclohexylmethyl-                                          N-(2-furoyl)]-amide     m.p.: 80-81° C.                                4-methyl-1,2,3-thiadiazole-5-                                                 carboxylic acid-[N-cyclohexylmethyl]                                          N-(2,4-dichlorobenzoyl)]-amide                                                                        m.p.: 87-88° C.                                4-methyl-1,2,3-thiadiazole-5-                                                 carboxylic acid-[N-cyclohexylmethyl-                                          N-(2-trifluoromethylbenzoyl)]-amide                                                                   m.p.: 63-64° C.                                4-methyl-1,2,3-thiadiazole-5-                                                 carboxylic acid-[N-cyclohexylmethyl]                                          N-(3,6-dichloro-2-methoxybenzoyl)]-amide                                                              m.p.: 76-77° C.                                4-methyl-1,2,3-thiadiazole-5-                                                 carboxylic acid-[N-cyclohexylmethyl-                                          N-(3-triflurormethylbenzoyl)]-amide                                                                   m.p.: 92-93° C.                                4-methyl-1,2,3-thiadiazole-5-                                                 carboxylic acid-[N-cyclohexylmethyl-                                          N-(3-furoyl)]-amide     m.p.: 86-88° C.                                4-methyl-1,2,3-thiadiazole-5-                                                 carboxylic acid-[N-cyclohexylmethyl-                                          N-(2,5-dichlorobenzoyl)]-amide                                                                        m.p.: 67-69° C.                                4-methyl-1,2,3-thiadiazole-5-                                                 carboxylic acid-[N-cyclohexylmethyl-                                          N-(3,5-dichlorobenzoyl)]-amide                                                                        m.p.: 67-69° C.                                4-methyl-1,2,3-thiadiazole-5-                                                 carboxylic acid-[ N-cyclohexylmethyl-                                         N-(2-phenoxybenzoyl)]-amide                                                                           m.p.: 91-93° C.                                4-methyl-1,2,3-thiadiazole-5-carboxy-                                         lic acid-[N-cyclohexylmethyl-N-(4-                                            methyl-1,2,3-thiadiazole-5-ylcarbonyl)]-                                      amide                   m.p.: 64-67° C.                                4-methyl-1,2,3-thiadiazole-5-                                                 carboxylic acid-[4-cyclohexyl-                                                methyl-N-(3,4-dichlorobenzoyl)]-                                              amide                   m.p.: 113-114° C.                              4-methyl-1,2,3-thiadiazole-5-                                                 carboxylic acid-[N-acetyl-N-                                                  (3-methylcyclohexyl)]-amide                                                                           m.p.: 68-70° C.                                ______________________________________                                    

STARTING PRODUCT

By way of example the making of one of the starting products used in theprocesses for making the compounds of the invention is done as follows:

4-methyl-1,2,3-thiadiazole-5-(N-cyclohexylmethylcarboximidechloride

47.8 g (0.2 mol) of 4-methyl-1,2,3-thiadiazole-5-carboxylicacid-(cyclohexylmethyl)-amide, dissolved in 100 ml toluene were reactedat room temperature with 41.6 (0.02 mol) of phosphorus pentachloride andsubsequently heated for 1 hour from reflux. The solution was thenconcentrated and the remaining oil was digested with cyclohexane.Recrystallization was effected from cyclohexane.

Yield: 40.0 g=77.5% of the theoretical value

M.p.: 51°-52° C.--colorless crystals.

USES AND ACTIVITIES

The following examples will further explain the use and activity andsuperiority of the compounds of the invention.

EXAMPLE 4

The compounds listed in the table below were sprayed in a hothouse inthe form of an aqueous emulsion or suspension in amounts of 5 kg ofactive agent/ha in 600 liters water/ha. The test plants sprayed were thefollowing: Sinapis (Si), Solanum (So), Beta vulgaris (Be), Gossypium(Go), Hordeum (Ho), Zea mays (Ze), Lolium (Lo), and Setaria (Se). Theapplication was effected either in preemergence application (V) or inpostemergence application (N). An evaluation of the results was effected3 weeks after the treatment on a scale from 0 to 4 as follows:

    __________________________________________________________________________                          Si  So  Be  Go  Ho  Ze  Lo  Se                          Compounds             V N V N V N V N V N V N V N V N                         __________________________________________________________________________    4-methyl-1,2,3-thiadiazole-5-                                                 carboxylic acid-(N-acetyl-N-                                                                        4 4 4 4 4 4 3 4 3 2 2 2 4 3 4 4                         cyclohexylmethyl)-amide                                                       4-methyl-1,2,3-thiadiazole-5-                                                 carboxylic acid-(N-benzoyl-                                                                         4 4 3 3 3 4 2 2 2 1 2 1 3 1 2 4                         N-cyclohexylmethyl)-amide                                                     4-methyl-1,2,3-thiadiazole-5-                                                 carboxylic acid-(N-isobutyryl-                                                                      3 4 3 4 3 4 2 4 3 0 2 0 2 1 2 4                         N-cyclohexylmethyl)-amide                                                     4-methyl-1,2,3-thiadiazole-5-                                                 carboxylic acid-(N-benzoyl-                                                                         0 3 0 2 0 2 0 1 0 1 0 1 0 0 0 4                         N-benzyl)-amide                                                               4-methyl-1,2,3-thiadiazole-5-                                                 carboxylic acid-[N-benzoyl-N-                                                                       0 1 0 1 0 1 0 0 0 0 0 0 0 0 0 1                         (4-fluorobenzyl)]-amide                                                       4-methyl-1,2,3-thiadiazole-5-                                                 carboxylic acid-[N-benzoyl-N-                                                                       0 1 0 1 0 1 0 1 0 1 0 1 0 1 0 1                         (2-methylcyclohexyl)]-amide                                                   4-methyl-1,2,3-thiadiazole-5-                                                 carboxylic acid-[N-acetyl-N-                                                                        0 4 0 3 0 3 0 3 0 1 0 0 0 1 0 4                         (2-fluorobenzyl)]-amide                                                       4-methyl-1,2,3-thiadiazole-5-                                                 carboxylic acid-[N-acetyl-N-                                                                        0 4 0 3 0 3 0 3 0 1 0 1 0 2 0 4                         (4-fluorobenzyl)]-amide                                                       4-methyl-1,2,3-thiadiazole-5-                                                 carboxylic acid-[N-acetyl-N-                                                                        1 4 0 2 0 2 0 1 0 0 0 0 0 0 0 4                         (4-chlorobenzyl)]-amide                                                       4-methyl-1,2,3-thiadiazole-5-                                                 carboxylic acid-]N-(4-chloro-                                                                       0 3 0 0 0 0 0 0 0 1 0 0 0 0 0 3                         benzoyl)-N-cyclohexylmethyl]-                                                 amide                                                                         4-methyl-1,2,3-thiadiazole-5-                                                 carboxylic acid-(N-propionyl-                                                                       3 4 3 3 1 4 0 4 3 1 1 1 1 1 2 4                         N-cyclohexylmethyl)-amide                                                     4-methyl-1,2,3-thiadiazole-5-                                                 carboxylic acid-[N-(4-fluorobenzo-                                                                  0 2 0 0 0 2 0 0 0 0 0 0 0 0 0 2                         yl)-N-cyclohexylmethyl]-amide                                                 4-methyl-1,2,3-thiadiazole-5-                                                 carboxylic acid-(N-chloroacetyl-                                                                    4 4 4 4 4 4 3 4 4 1 3 1 4 3 4 4                         N-cyclohexylmethyl)-amide                                                     4-methyl-1,2,3-thiadiazole-5-                                                 carboxylic acid-[N-(3-chloro-                                                                       0 3 1 1 0 1 0 2 0 0 0 0 0 1 1 2                         benzoyl)-N-cyclohexylmethyl]-                                                 amide                                                                         4-methyl-1,2,3-thiadiazole-5-                                                 carboxylic acid-[N-(3-methyl-                                                                       0 4 1 3 0 1 0 2 1 0 0 0 1 0 1 3                         benzoyl-N-cyclohexylmethyl)]-amide                                            4-methyl-1,2,3-thiadiazole-5-                                                 carboxylic acid-[N-(4-methyl-                                                                       1 3 1 3 0 1 0 1 0 1 0 0 0 1 0 3                         benzoyl)-N-cyclohexylmethyl]-amide                                            4-methyl-1,2,3-thiadiazole-5-                                                 carboxylic acid-(N-valeryl-N-cy-                                                                    4 4 4 3 4 4 3 4 3 1 2 1 3 2 4 4                         clohexylmethyl)-amide                                                         4-methyl-1,2,3-thiadiazole-5-                                                 carboxylic acid-[N-(2,4-di-                                                                         4 4 4 4 4 4 3 3 3 0 3 1 4 1 4 4                         chlorophenoxyacetyl)-N-                                                       cyclohexylmethyl]-amide                                                       4-methyl-1,2,3-thiadiazole-5-                                                 carboxylic acid-(N-benzoyl-N-                                                                       0 1 0 2 0 2 0 0 0 0 0 0 0 0 0 2                         cyclohexyl)-amide                                                             4-methyl-1,2,3-thiadiazole-5-                                                 carboxylic acid-(N-acetyl-N-                                                                        0 1 1 1 0 1 0 1 1 1 0 1 0 0 0 1                         cyclohexyl)-amide                                                             4-methyl-1,2,3-thiadiazole-5-                                                 carboxylic acid-[N(2-chloro-                                                                        0 1 0 1 1 2 0 1 0 0 0 1 0 1 0 2                         benzoyl)-N-cyclohexylmethyl]-                                                 amide                                                                         4-methyl-1,2,3-thiadiazole-5-                                                 carboxylic acid-(N-cinnamoyl-N-                                                                     2 3 3 3 3 4 2 2 1 2 0 1 3 3 3 4                         cyclohexylmethyl)-amide                                                       4-methyl-1,2,3-thiadiazole-5-                                                 carboxylic acid-(N-cyclohexylcar-                                                                   0 1 1 1 2 2 0 1 0 1 0 0 1 0 0 1                         bonyl-N-cyclohexylmethyl)-amide                                               4-methyl-1,2,3-thiadiazole-5-                                                 carboxylic acid-(N-cyclohexylmethyl-                                                                4 4 3 3 3 4 2 2 2 1 0 0 1 2 3 4                         N-cyclopropylcarbonyl)-amide                                                  4-methyl-1,2,3-thiadiazole-5-                                                 carboxylic acid-[N-cyclohexylmethyl-                                                                3 2 3 3 3 4 2 2 1 1 1 1 1 2 3 4                         N-(2,6-dichlorobenzoyl)]-amide                                                4-methyl-1,2,3-thiadiazole-5-                                                 carboxylic acid-(N-cyclohexylmethyl-                                                                4 4 4 3 4 4 3 4 4 2 3 2 4 3 4 4                         N-dichloroacetyl)-amide                                                       4-methyl-1,2,3-thiadiazole-5-                                                 carboxylic acid-(N-crotonoyl-N-                                                                     4 4 4 3 2 3 3 4 3 1 2 0 4 1 3 3                         cyclohexylmethyl)-amide                                                       4-methyl-1,2,3-thiadiazole-5-                                                 carboxylic acid-[(N-cyclohexylmethyl-                                                               2 4 3 3 2 4 0 3 0 3 2 0 3 0 3 2                         N-(2-furoyl)]-amide                                                           4-methyl-1,2,3-thiadiazole-5-                                                 carboxylic acid-[(N-cyclohexylmethyl-                                                               1 1 1 1 0 0 0 0 0 0 0 0 0 0 0 0                         N-(2,4-dichlorobenzoyl)]-amide                                                4-methyl-1,2,3-thiadiazole-5-                                                 carboxylic acid-[N-cyclohexylmethyl-                                                                0 0 0 0 0 0 0 1 0 0 0 0 0 0 0 1                         N-(2-trifluoromethylbenzoyl]-amide                                            4-methyl-1,2,3-thiadiazole-5-carbox-                                          ylic acid-[N-cyclohexylmethyl-N-                                                                    3 3 3 3 3 3 2 4 2 0 1 1 2 0 1 2                         (3,6-dichloro-2-methoxybenzoyl)]-                                             amide                                                                         4-methyl-1,2,3-thiadiazole-5-carbox-                                          ylic acid-[N-cyclohexylmethyl-N-                                                                    1 3 2 2 0 1 0 2 0 0 0 0 0 0 0 1                         (3-trifluoromethylbenzoyl)]-                                                  amide                                                                         4-methyl-1,2,3-thiadiazole-5-carbox-                                          ylic acid-[N-cyclohexylmethyl-N-                                                                    2 4 4 2 0 3 0 2 2 0 0 0 0 1 2 0                         (3-furoyl)]-amide                                                             4-methyl-1,2,3-thiadiazole-5-carbox-                                          ylic acid-[N-cyclohexylmethyl-N-                                                                    0 1 0 1 0 1 0 0 0 0 0 0 0 0 0 0                         (2,5-dichlorobenzoyl)]-amide                                                  4-methyl-1,2,3-thiadiazole-5-carbox-                                          ylic acid-[N-cyclohexylmethyl-N-                                                                    2 1 4 2 2 0 0 0 1 0 1 0 2 0 2 0                         (3,5-dichlorobenzoyl)]-amide                                                  4-methyl-1,2,3-thiadiazole-5-carbox-                                          ylic acid-[N-cyclohexylmethyl-N-(2-                                                                 0 1 0 1 0 1 0 0 0 0 0 0 0 0 0 0                         phenoxybenzoyl)]-amide                                                        4-methyl-1,2,3-thiadiazole-5-carbox-                                          ylic acid-[N-cyclohexylmethyl-N-                                                                    4 4 4 4 4 4 4 4 4 4 3 4 4 4 4 4                         (4-methyl-1,2,3-thiadiazole-5-ylcar-                                          bonyl)]-amide                                                                 4-methyl-1,2,3-thiadiazole-5-carbox-                                          ylic acid-[N-cyclohexylmethyl-N-(3,4-                                                               4 4 4 4 4 4 4 4 4 4 3 3 4 4 4 4                         dichlorobenzoyl)]-amide                                                       4-methyl-1,2,3-thiadiazole-5-                                                 carboxylic acid-[N-acetyl-N-(3-                                                                     4 4 4 4 4 4 4 4 4 4 4 3 4 4 4 4                         methylcyclohexyl)]-amide                                                      Untreated             0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0                         __________________________________________________________________________     0 = no effects                                                                1-2 = growth regulating effect in the form of an intensive coloration of      the leaves, retardation, growth depression and smaller or larger size of      the leaves as well as low root development.                                   3-4 = these plants were no longer viable or were withered.               

EXAMPLE 5

The plants listed below were treated in a hothouse prior to emergencewith the indicated compound in an amount of 1 kg of active agent/ha. Thecompound was applied for this purpose as a suspension in 500 liters ofwater/ha to the soil and the application was effected in a uniformmanner. The results show that the compounds of the invention destroyedwidespread weeds while they left without damage the economicallyimportant soybeans.

The results were recorded on a scale from 0 to 10 in which 0 indicatedtotal destruction of the plants and 10 indicated no damage to theplants.

    __________________________________________________________________________               soy-         Alope-                                                                            Echino-  Digi-                                    Compound   beans                                                                             Ipomoea                                                                            Avena                                                                             curus                                                                             chloa                                                                              Setaria                                                                           taria                                                                             Poa                                                                              Solanum                                                                            Datura                                                                            Escholtzia                                                                          Kochia             __________________________________________________________________________    4-methyl-1,2,3-                                                               thiadiazole-5-car-                                                                       10   0    0   0   0    0   0   0  0    0   0     0                 boxylic acid-(N-                                                              acetyl-N-cyclohexyl-                                                          methyl)-amide                                                                 Untreated  10  10   10  10  10   10  10  10 10   10  10    10                 __________________________________________________________________________

EXAMPLE 6

Cucumbers were treated in a hothouse prior to emergence with thecompound listed below in amounts of 0.3 kg, 1 kg and 3 kg/ha. The activeagents for this purpose were applied as a 20% emulsion concentrate in anaqueous emulsion with an amount of liquid of 500 liters spray perhectare. 3 weeks after treatment the growth regulating effect wasdetermined by measuring the length and width of the first foliage leaf.The results of the measurement were related to those obtained inuntreated control plants. As appears from the measurements the treatmentwith the compound of the invention resulted in a great enlargement ofthe leaf. Besides, the treated plants were of a more intensive green.

    ______________________________________                                                         active   length   width                                                       agent    of leaf  of leaf                                    Compound         kg/ha    in %     in %                                       ______________________________________                                        4-methyl-1,2,3-thia-                                                                           0.3      110      107                                        diazole-5-carboxylic                                                                           1.0      124      130                                        acid-(N-acetyl-N-                                                                              3.0      133      151                                        cyclohexylmethyl)-amide                                                       Untreated        --       100      100                                        ______________________________________                                    

EXAMPLE 7 Effects of a prophylactic leaf treatment of grapevines againstPlasmopara viticola

Young grapevines with about 5 to 8 leaves were sprayed in a hothousewith the compounds listed below in the concentrations indicated. Afterthe spray deposit had been dried the bottom side of the leaves wassprayed with an aqueous emulsion of sporangia of the above-indicatedfungus (about 20,000 per ml). The plants were then immediately incubatedin a hothouse at 22° to 24° C. and in as high a water-saturatedatmosphere as possible.

Starting with the second day the air humidity was reduced for 3 to 4days to a normal level (30 to 70% saturation) followed by another day inwater vapor saturation. Following this treatment the percentage portionof the fungus infected surface of each leaf was noted and the averageobtained per treatment was saturated as follows in order to determinethe fungicidal activity: ##EQU1##

The active agents were applied in the form of a 20% spray powder.

    ______________________________________                                                          results after treatment                                                       with following percentage                                                     of compound                                                 Compound            0.025     0.005                                           ______________________________________                                        4-methyl-1,2,3-thiadiazole-5-                                                 carboxylic acid-(N-benzoyl-N-                                                                     100       95                                              cyclohexylmethyl)-amide                                                       4-methyl-1,2,3-thiadiazole-5-                                                 carboxylic acid-(N-benzoyl-N-                                                                     100       49                                              benzyl)-amide                                                                 4-methyl-1,2,3-thiadiazole-5-                                                 carboxylic acid-[N-benzoyl-N-                                                                     77                                                        (2-methylcyclohexyl)]-amide                                                   4-methyl-1,2,3-thiadiazole-5-                                                 carboxylic acid-[N-acetyl-N-  97                                              (2-fluorobenzyl)]-amide                                                       4-methyl-1,2,3-thiadiazole-5-                                                 carboxylic acid-[N-acetyl-N-  73                                              (4-fluorobenzyl)]-amide                                                       4-methyl-1,2,3-thiadiazole-5-                                                 carboxylic acid-[N-acetyl-N-  78                                              (4-chlorobenzyl)]-amide                                                       4-methyl-1,2,3-thiadiazole-5-                                                 carboxylic acid-(N-chloroacetyl-                                                                            97                                              N-cyclohexylmethyl)-amide                                                     4-methyl-1,2,3-thiadiazole-5-                                                 carboxylic acid-(N-valeryl-N-cy-                                                                            99                                              clohexylmethyl)-amide                                                         4-methyl-1,2,3-thiadiazole-5-                                                 carboxylic acid-[N-(2-chlorobenzo-                                            yl)-N-cyclohexylmethyl]-amide                                                                     75                                                        4-methyl-1,2,3-thiadiazole-5-                                                 carboxylic acid-(N-cinnamoyl-N-                                                                   75                                                        cyclohexylmethyl)-amide                                                       4-methyl-1,2,3-thiadiazole-5-                                                 carboxylic acid-(N-cyclohexylmethyl-                                                              70                                                        N-cyclopropylcarbonyl)-amide                                                  4-methyl-1,2,3-thiadiazole-5-                                                 carboxylic acid-[N-cyclohexyl-                                                                    75                                                        methyl-N-(2,6-dichlorobenzoyl)]-                                              amide                                                                         ______________________________________                                    

EXAMPLE 8 Effect of the prophylactic leaf treatment of pumpkin plantsagainst Erysiphe cichoracearum

The compounds noted below were sprayed in the indicated concentrationson young pumpkin plants until they were dripping wet.

After the spray deposits had been dried the plants were inoculated bybeing dusted with dry mildew spores of Erysiphe cichoracearum at atemperature of 24° C.

After a week the infested mildew surface in percentage was determinedrelative to the total leaf surface. The fungicidal activity wascalculated as follows: ##EQU2##

The active compounds were applied in the form of a 20% spray powder.

    ______________________________________                                                          results after treatment                                                       with following percentage                                                     of compound                                                 Compound            0.025     0.005                                           ______________________________________                                        4-methyl-1,2,3-thiadiazole-5-                                                 carboxylic acid-(N-acetyl-N-cy-                                                                   100       92                                              clohexylmethyl)-amide                                                         4-methyl-1,2,3-thiadiazole-5-                                                 carboxylic acid-(N-benzoyl-N-                                                                     70                                                        cyclohexylmethyl)-amide                                                       4-methyl-1,2,3-thiadiazole-5-                                                 carboxylic acid-(N-isobutyryl-N-                                                                  100       93                                              cyclohexylmethyl)-amide                                                       4-methyl-1,2,3-thiadiazole-5-                                                 carboxylic acid-(N-propionyl-N-                                                                   85        60                                              cyclohexylmethyl)-amide                                                       4-methyl-1,2,3-thiadiazole-5-                                                 carboxylic acid-(N-chloroacetyl-                                                                  99        85                                              N-cyclohexylmethyl)-amide                                                     4-methyl-1,2,3-thiadiazole-5-                                                 carboxylic acid-(N-valeryl-N-                                                                     100       90                                              cyclohexylmethyl)-amide                                                       4-methyl-1,2,3-thiadiazole-5-                                                 carboxylic acid-[N-(2,4-dichloro-                                                                 60                                                        phenoxyacetyl)-N-cyclohexyl-                                                  methyl]-amide                                                                 4-methyl-1,2,3-thiadiazole-5-                                                 carboxylic acid-(N-cyclohexylmethyl-                                                              80                                                        N-cyclopropylcarbonyl)-amide                                                  ______________________________________                                    

It is noted that none of the treatments did any damage to the pumpkinplants.

EXAMPLE 9 Effect of leaf treatment of rice seedlings against Piriculariaoryzae

Young rice seedlings were sprayed with the compounds listed below in theindicated amounts until they were dripping wet. After drying of thespray deposits the treated plants and untreated control plants wereinoculated by being sprayed with a suspension of spores (about200,000/ml) of the fungus that causes the leaf spot disease, Piriculariaoryzae. The incubation was carried out of the wet plants in a hothouseat +25° to +27° C.

After 5 days it was determined which percentage of the leaf surface hadbeen infested. From the figures obtained the fungicidal activity wasdetermined as follows: ##EQU3##

The active agents were applied in the form of a 20% spray powder.

    ______________________________________                                                            results after treatment                                                       with following percentage                                                     of compound                                               Compound            0.1                                                       ______________________________________                                        4-methyl-1,2,3-thiadiazole-5-                                                 carboxylic acid-(N-benzoyl-N-                                                                     75                                                        cyclohexylmethyl)-amide                                                       4-methyl-1,2,3-thiadiazole-5-                                                 carboxylic acid-(N-benzoyl-N-                                                                     90                                                        benzyl)-amide                                                                 4-methyl-1,2,3-thiadiazole-5-                                                 carboxylic acid-[N-benzoyl-N-                                                                     75                                                        (2-methylcyclohexyl]-amide                                                    4-methyl-1,2,3-thiadiazole-5-                                                 carboxylic acid-(N-chloroacetyl-                                                                  90                                                        N-cyclohexylmethyl)-amide                                                     ______________________________________                                    

It is noted that none of the rice plants was damaged by the treatment.

EXAMPLE 10 Effect of seed treatment of barley against Helminthosporiumspec

Barley seeds which had a natural infestation by Helminthosporiumgramineum were in some cases left untreated and in other cases treatedwith the compound as indicated in the table below and were seeded inplant pots filled with earth. The germination was effected attemperatures below +16° C. After emergence the seedlings were exposeddaily for 12 hours to artificial light. After about 5 weeks all emergedplants including the fungus infected plants were counted as per eachtest plant. The fungicidal activity was calculated as follows: ##EQU4##

The compounds were applied in the form of a 20% spray powder.

    ______________________________________                                                      % effect with following                                                       amounts (in g) of active agent                                                per 100 kg of seed material                                     Compound        10      2      13.1  5.3  2.6                                 ______________________________________                                        4-methyl-1,2,3-thiadiazole-5-                                                 carboxylic acid-(N-acetyl-N-                                                                  100     70                                                    cyclohexylmethyl)-amide                                                       Comparison compound                                                           methoxyethyl-mercury-          96    86   70                                  silicate                                                                      ______________________________________                                    

EXAMPLE 11 Effect of seed treatment of wheat against Tilletia caries

Wheat seeds were contaminated with 3 g per kg of spores of the stinkingsmuts fungus Tilletia caries. Untreated grains as well as grain treatedwith the compounds listed below were then pressed with their tuft endinto Petri dishes filled with moist loam and were incubated attemperatures below +12° C. for a period of 3 days. The grains were thenremoved and the Petri dishes with the remaining spores of the stinkingsmuts were further incubated at about +12° C.; after 10 days the sporeswere examined regarding germination. The fungicidal effect wascalculated as follows: ##EQU5##

The compounds were applied in the form of a 20% spray powder.

    ______________________________________                                                            % action of                                                                   20 g active agent                                         Compounds           per 100 kg of seed material                               ______________________________________                                        4-methyl-1,2,3-thiadiazole-5-                                                 carboxylic acid-(N-chloroacetyl-                                                                  75                                                        N-cyclohexylmethyl)-amide                                                     4-methyl-1,2,3-thiadiazole-5-                                                 carboxylic acid-(N-valeryl-N-                                                                     75                                                        cyclohexylmethyl)-amide                                                       4-methyl-1,2,3-thiadiazole-5-                                                 carboxylic acid-[N-(2,4-dichlorphen-                                                              75                                                        oxyacetyl)-N-cyclohexylmethyl]-                                               amide                                                                         4-methyl-1,2,3-thiadiazole-5-                                                 carboxylic acid-[N-(2-chloro-                                                                     84                                                        benzoyl)-N-cyclohexylmethyl]-                                                 amide                                                                         4-methyl-1,2,3-thiadiazole-5-                                                 carboxylic acid-(N-cinnamoyl-N-                                                                   80                                                        cyclohexylmethyl)-amide                                                       4-methyl-1,2,3-thiadiazole-5-                                                 carboxylic acid-(N-cyclohexylcar-                                                                 82                                                        bonyl-N-cyclohexylmethyl)-amide                                               4-methyl-1,2,3-thiadiazole-5-                                                 carboxylic acid-(N-cyclohexylmethyl-                                                              90                                                        N-cyclopropylcarbonyl)-amide                                                  ______________________________________                                    

EXAMPLE 12

Cotton leaves at the stage of 6-7 fully developed leaves were sprayedfour times with the below listed compound as an aqueous emulsion orsuspension in an amount of 500 l water/ha. The number of leaves droppedafter 9 days is shown below as the percentage of the initial leaves.

    ______________________________________                                        Compound          kg/ha     % defoliation                                     ______________________________________                                        4-methyl-1,2,3-thiadiazole-                                                   5-carboxylic acid-(N-acetyl-                                                                    0.5       76.9                                              N-cyclohexylmethyl)-amide                                                     Comparison compound                                                           Tri-n-butyl-trithiophosphate                                                                    0.5       65.4                                              ______________________________________                                    

EXAMPLE 13

Cotton plants at the stage of 5 to 6 fully developed foliage leaves weresprayed with the compounds listed below in the concentrations indicated.The compounds were applied in the form of an aqueous emulsion orsuspension in amounts of 0.5 kg in 500 liter water/ha. The treatment wasrepeated 4 times. In the following table the dropped leaves were countedafter 14 days as a percentage of all leaves existing when the treatmentcommenced.

    ______________________________________                                        Compound           kg/ha     % leaf drop                                      ______________________________________                                        4-methyl-1,2,3-thiadiazole-                                                   5-carboxylic acid-(N-chloro-                                                                     0.5       81.0                                             acetyl)-amide                                                                 4-methyl-1,2,3-thiadiazole-                                                   5-carboxylic acid-(N-valeryl-                                                                    0.5       81.0                                             N-cyclohexylmethyl)-amide                                                     4-methyl-1,2,3-thiadiazole-                                                   5-carboxylic acid-(N-isobutyryl-                                                                 0.5       66.7                                             N-cyclohexylmethyl)-amide                                                     ______________________________________                                    

Without further analysis, the foregoing will so fully reveal the gist ofthe present invention that others can, by applying current knowledge,readily adapt it for various applications without omitting featuresthat, from the standpoint of prior art, fairly constitute essentialcharacteristics of the generic or specific aspects of this invention.

What is claimed as new and desired to be protected by Letters Patent isset forth in the appended claims.
 1. 1,2,3-thiadiazole-5-carboxylic acidamide derivatives of the formula ##STR16## wherein R₁ is methyl,R₃ CO isacetyl, crotonyl, chloroacetyl, dichloroacetyl, propionyl, isobutyryl,valeryl, cinnamoyl, furoyl, 4-methyl-1,2,3-thiadiazol-5-ylcarbonyl,cyclopropylcarbonyl, cyclohexylcarbonyl, dichlorophenoxyacetyl,phenoxybenzoyl, benzoyl, halobenzoyl, dichlorobenzoyl,dichloromethoxybenzoyl, methylbenzoyl or trifluoromethylbenzoyl, and R₂is benzyl, halobenzyl, cyclohexyl, methylcyclohexyl or cyclohexylmethyl.2. The compounds of claim 1 whereinR₁ is methyl R₃ CO is acetyl,chloroacetyl, propionyl, valeryl, cinnamoyl, cyclohexylcarbonyl,dichlorophenoxyacetyl, benzoyl, halobenzoyl, dichlorobenzoyl ormethylbenzoyl, and R₂ is benzyl, halobenzyl, cyclohexyl,methylcyclohexyl or cyclohexylmethyl.
 3. The compound of claim 1 whichis 4-methyl-1,2,3-thiadiazole-5-carboxylicacid-(N-acetyl-N-cyclohexylmethyl)-amide.
 4. The compound of claim 1which is 4-methyl-1,2,3-thiadiazole-5-carboxylicacid-(N-benzoyl-N-cyclohexylmethyl)-amide.
 5. The compound of claim 1which is 4-methyl-1,2,3-thiadiazole-5-carboxylicacid-(N-isobutyryl-N-cyclohexylmethyl)-amide.
 6. The compound of claim 1which is 4-methyl-1,2,3-thiadiazole-5-carboxylicacid-(N-benzonyl-N-benzyl)-amide.
 7. The compound of claim 1 which is4-methyl-1,2,3-thiadiazole-5-carboxylicacid-[N-benzoyl-N-(4-fluorobenzyl)]-amide.
 8. The compound of claim 1which is 4-methyl-1,2,3-thiadiazole-5-carboxylicacid-[N-benzoyl-N-(2-methylcyclohexyl)]-amide.
 9. The compound of claim1 which is 4-methyl-1,2,3-thiadiazole-5-carboxylicacid-[N-acetyl-N-(2-fluorobenzyl)]-amide.
 10. The compound of claim 1which is 4-methyl-1,2,3-thiadiazole-5-carboxylicacid-[N-acetyl-N-(4-fluorobenzyl)]-amide.
 11. The compound of claim 1which is 4-methyl-1,2,3-thiadiazole-5-carboxylicacid-[N-acetyl-N-(4-chlorobenzyl)]-amide.
 12. The compound of claim 1which is 4-methyl-1,2,3-thiadiazole-5-carboxylicacid-[N-(4-chlorobenzoyl)-N-cyclohexylmethyl]-amide.
 13. The compound ofclaim 1 which is 4-methyl-1,2,3-thiadiazole-5-carboxylicacid-(N-propionyl-N-cyclohexylmethyl)-amide.
 14. The compound of claim 1which is 4-methyl-1,2,3-thiadiazole-5-carboxylicacid-[N-(4-fluorobenzoyl)-N-cyclohexylmethyl]-amide.
 15. The compound ofclaim 1 which is 4-methyl-1,2,3-thiadiazole-5-carboxylicacid-(N-chloroacetyl-N-cyclohexylmethyl)-amide.
 16. The compound ofclaim 1 which is 4-methyl-1,2,3-thiadiazole-5-carboxylicacid-[N-(3-chlorobenzoyl)-N-cyclohexylmethyl]-amide.
 17. The compound ofclaim 1 which is 4-methyl-1,2,3-thiadiazole-5-carboxylicacid-[N-(3-methylbenzoyl)-N-cyclohexylmethyl]-amide.
 18. The compound ofclaim 1 which is 4-methyl-1,2,3-thiadiazole-5-carboxylicacid-[N-(4-methylbenzoyl)-N-cyclohexylmethyl]-amide.
 19. The compound ofclaim 1 which is 4-methyl-1,2,3-thiadiazole-5-carboxylicacid-(N-valeryl-N-cyclohexylmethyl)-amide.
 20. The compound of claim 1which is 4-methyl-1,2,3-thiadiazole-5-carboxylicacid-[N-(2,4-dichlorophenoxyacetyl)-N-cyclohexylmethyl]-amide.
 21. Thecompound of claim 1 which is 4-methyl-1,2,3-thiadiazole-5-carboxylicacid-(N-benzoyl-N-cyclohexyl)-amide.
 22. The compound of claim 1 whichis 4-methyl-1,2,3-thiadiazole-5-carboxylicacid-(N-acetyl-N-cyclohexyl)-amide
 23. The compound of claim 1 which is4-methyl-1,2,3-thiadiazole-5-carboxylicacid-[N-(2-chlorobenzoyl)-N-cyclohexylmethyl]-amide.
 24. The compound ofclaim 1 which is 4-methyl-1,2,3-thiadiazole-5-carboxylicacid-(N-cinnamoyl-N-cyclohexylmethyl)-amide.
 25. The compound of claim 1which is 4-methyl-1,2,3-thiadiazole-5-carboxylicacid-(N-cyclohexylcarbonyl-N-cyclohexylmethyl)-amide.
 26. The compoundof claim 1 which is 4-methyl-1,2,3-thiadiazole-5-carboxylicacid-(N-cyclohexylmethyl-N-cyclopropylcarbonyl)-amide.
 27. The compoundof claim 1 which is 4-methyl-1,2,3-thiadiazole-5-carboxylicacid-[N-cyclohexylmethyl-N-(2,6-dichlorobenzoyl)]-amide.
 28. Thecompound of claim 1 which is 4-methyl-1,2,3-thiadiazole-5-carboxylicacid-(N-cyclohexylmethyl-N-dichloroacetyl)-amide.
 29. The compound ofclaim 1 which is 4-methyl-1,2,3-thiadiazole-5-carboxylicacid-(N-crotonoyl-N-cyclohexylmethyl)-amide.
 30. The compound of claim 1which is 4-methyl-1,2,3-thiadiazole-5-carboxylicacid-[N-cyclohexylmethyl-N-(2-furoyl)]-amide.
 31. The compound of claim1 which is 4-methyl-1,2,3-thiadiazole-5-carboxylicacid-[N-cyclohexylmethyl-N-(2,4-dichlorobenzoyl)]-amide.
 32. Thecompound of claim 1 which is 4-methyl-1,2,3-thiadiazole-5-carboxylicacid-[N-cyclohexylmethyl-N-(2-trifluoromethylbenzoyl)]-amide.
 33. Thecompound of claim 1 which is 4-methyl-1,2,3-thiadiazole-5-carboxylicacid-[N-cyclohexylmethyl-N-(3,6-dichloro-2-methoxybenzoyl)]-amide. 34.The compound of claim 1 which is 4-methyl-1,2,3-thiadiazole-5-carboxylicacid-[N-cyclohexylmethyl-N-(3-trifluoromethylbenzoyl)]-amide.
 35. Thecompound of claim 1 which is 4-methyl-1,2,3-thiadiazole-5-carboxylicacid-[N-cyclohexylmethyl-N-(3-furoyl)]-amide.
 36. The compound of claim1 which is 4-methyl-1,2,3-thiadiazole-5-carboxylicacid-[N-cyclohexylmethyl-N-(2,5-dichlorobenzoyl)]-amide.
 37. Thecompound of claim 1 which is 4-methyl-1,2,3-thiadiazole-5-carboxylicacid-[N-cyclohexylmethyl-N-(3,5-dichlorobenzoyl)]-amide.
 38. Thecompound of claim 1 which is 4-methyl-1,2,3-thiadiazole-5-carboxylicacid-[N-cyclohexylmethyl-N-(2-phenoxybenzoyl)]-amide.
 39. The compoundof claim 1 which is 4-methyl-1,2,3-thiadiazole-5-carboxylicacid-[N-cyclohexylmethyl-N-(4-methyl-1,2,3-thiadiazole-5-ylcarbonyl)]-amide.40. The compound of claim 1 which is4-methyl-1,2,3-thiadiazole-5-carboxylicacid-[N-cyclohexylmethyl-N-(3,4-dichlorobenzoyl)]-amide.
 41. Thecompound of claim 1 which is 4-methyl-1,2,3-thiadiazole-5-carboxylicacid-[N-acetyl-N-(3-methylcyclohexyl)]-amide.
 42. A composition havingherbicidal, growth regulating and defoliating activity in which at leastone of the active agents is a compound as defined in claim 1, the saidactive agent being present in amounts of about 5 to 95% by weight, thecomposition including about 95 to 5% by weight of liquid or solidcarrier materials.
 43. The composition of claim 42 which includes up to20% by weight of surface active agents with a corresponding reduction ofthe amount of liquid or solid carrier materials.
 44. A compositionhaving fungicidal activity comprising at least one active agent asdefined in claim 1 in amounts of about 5 to 90% by weight, liquid orsolid carrier materials being present in an amount of about 95 to 5% byweight.
 45. The composition of claim 44 which includes up to 20% ofsurface active agents with a corresponding reduction of the liquid orsolid carrier materials.